JMZ-1S, a CHA-containing molecular sieve and methods of preparation

Abstract

JMZ-1S, a silicoaluminophosphate molecular sieve having a CHA structure and containing a trimethyl(cyclohexylmethyl)ammonium cation cation is described. A calcined product, JMZ-1SC, formed from JMZ-1S is also described. Methods of preparing JMZ-1S, JMZ-1SC and metal containing calcined counterparts of JMZ-1SC are described along with methods of using JMZ-1SC and metal containing calcined counterparts of JMZ-1SC in treating exhaust gases and in converting methanol to olefines.

What is claimed is: 
     
       1. A molecular sieve comprising a CHA type framework type with phosphate within the framework, wherein the molecular sieve is silicoaluminophosphate, the molecular sieve having a SiO 2 /Al 2 O 3  (SAR) of between 0.45 and 0.55 inclusive, and a P 2 O 5 /Al 2 O 3  (PAR) ratio of between 0.75 and 0.85 inclusive. 
     
     
       2. The molecular sieve of  claim 1 , where the molecular sieve further comprises at least one extra-framework transition metal selected from the group consisting of Ag, Au, Ce, Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo, Nb, Ni, Pd, Pt, Re, Rh, Ru, Sn, Ta, V, W and Zn. 
     
     
       3. The molecular sieve of  claim 1 , where the molecular sieve is calcined or contains one or more structure directing agents (SDAs). 
     
     
       4. A molecular sieve of  claim 1 , comprising a CHA type framework type molecular sieve containing a structure directing agent (SDA) having a characteristic X-ray powder diffraction pattern comprising 2-theta positions at 9.47 (VS), 16.10 (S), 20.73 (VS), 24.51 (M) and 30.86 (M)±0.2 with the corresponding relative intensity shown in parenthesis. 
     
     
       5. A molecular sieve of  claim 4 , wherein the characteristic X-ray powder diffraction pattern further comprises 2-theta positions at 12.99 (W), 13.81 (W), 17.41 (W), 19.01 (W), 21.80 (W), 22.60 (W), 23.09 (W), 26.15 (W), 27.86 (W), 30.22 (W), 34.84 (W), 35.63(W)±0.2 with the corresponding relative intensity shown in parenthesis. 
     
     
       6. The molecular sieve of  claim 1  prepared by using a structure-directing agent comprising trimethyl(cyclohexylmethyl) ammonium cations. 
     
     
       7. A composition comprising a silicoaluminophosphate molecular sieve crystal having a CHA framework, as synthesized and in an anhydrous state, comprising a pentavalent phosphorus oxide, a trivalent aluminum oxide, a tetravalent silicon oxide, and having a trimethyl(cyclohexylmethyl) ammonium cation present in the crystal structure, wherein the molecular sieve crystal is free of substituted or unsubstituted 5,4-azonium anions and is free of ammonium anions having a substituents selected from bridged polycyclics, cycloaryls, heterocyclics, cycloalkyls other than cyclohexylmethyl, and C2-C4 alkyls. 
     
     
       8. A calcined zeolite comprising a framework structure comprising a CHA type framework with phosphate within the framework, where the molecular sieve is a silicoaluminophosphate, the molecular sieve having a SiO 2 /Al 2 O 3  (SAR) of between 0.45 to 0.55 inclusive, a P 2 O 5 /Al 2 O 3  (PAR) ratio of between 0.75 to 0.85 inclusive, and having a characteristic X-ray powder diffraction pattern comprising 2-theta positions at 9.57 (VS), 13.01 (M), 16.17 (W), 17.89 (W), 20.82 (M), 23.29 (W), 25.12 (W), 26.22 (W), 30.99 (W), 31.34 (W)±0.2 with the corresponding relative intensity shown in parenthesis, wherein the zeolite does not comprise a structure directing agent (SDA). 
     
     
       9. The calcined molecular sieve of  claim 8  wherein the calcined molecular sieve further comprises an exchanged metal. 
     
     
       10. The calcined molecular sieve of  claim 9 , where the exchanged metal is copper or iron. 
     
     
       11. The calcined molecular sieve of  claim 9  where the exchanged metal is copper. 
     
     
       12. A catalyst comprising a calcined molecular sieve according to  claim 9 . 
     
     
       13. The catalyst of  claim 12 , wherein the calcined molecular sieve further comprises a non-framework transition metal or noble metal. 
     
     
       14. The catalyst of  claim 13 , wherein the non-framework transition metal is selected from the group consisting of Cu, Fe, V, Co, Ni, Nb, Mo, Ta, Mn and W. 
     
     
       15. The catalyst of  claim 13 , wherein the non-framework transition metal is Cu or Fe. 
     
     
       16. The catalyst of  claim 13 , wherein the molecular sieve comprises about 0.1 to about 5 weight percent of the transition metal or noble metal. 
     
     
       17. The catalyst of  claim 13 , wherein the molecular sieve comprises about 0.1 to about 5 weight percent ionic copper. 
     
     
       18. The catalyst of  claim 13 , wherein the noble metal is selected from Pt, Pd, Ru, Rh, Os, Ir, Ag, or Au. 
     
     
       19. The catalyst of  claim 13 , further comprising Ca. 
     
     
       20. The catalyst of  claim 13 , further comprising Ce. 
     
     
       21. A catalyst article for treating exhaust gas comprising a catalyst of  claim 12  disposed on and/or within a honeycomb structure. 
     
     
       22. A method for synthesizing a molecular sieve of  claim 1 , the method comprising:
 a. forming heating a reaction mixture comprising: (a) at least one source of phosphate, (b) at least one source of alumina, (c) at least one source of silica, and (c) a structure directing agent (SDA) comprising trimethyl(cyclohexylmethyl) ammonium cation: and 
 b. forming molecular sieve crystals having a CHA framework and the structure directing agent, and 
 c. recovering at least a portion of the molecular sieve crystals from the mother liquor. 
 
     
     
       23. The method of  claim 22 , wherein the SDA is associated with an anion selected from the group consisting of fluoride, chloride, bromide, iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, carbonate and bicarbonate. 
     
     
       24. The method of  claim 22 , wherein the SDA is associated with an hydroxide anion. 
     
     
       25. The method of  claim 22 , wherein the reaction mixture is a gel having a molar compositional ratio of: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   P 2 O 5 /Al 2 O 3   
                   0.5-1   
                 
                     
                   SiO 2 /Al 2 O 3   
                   0.2-0.8 
                 
                     
                   SDA/Al 2 O 3   
                    0.1-1.50 
                 
                     
                   H 2 O/Al 2 O 3   
                    20-200 
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
               
            
           
         
         wherein R is the SDA. 
       
     
     
       26. The method of  claim 22 , wherein the reaction mixture further comprises from about 0.1 to about 10% w/w of seed crystals, wherein the seed crystals comprise a crystalline molecular sieve having a CHA framework. 
     
     
       27. The method of  claim 26 , wherein the seed crystals comprise from 1 to 40 weight percent of at least one crystalline molecular sieve impurity. 
     
     
       28. A composition prepared by the method of  claim 22  for synthesizing a molecular sieve of  claim 1 , the method comprising:
 a. forming heating a reaction mixture comprising: (a) at least one source of phosphate, (b) at least one source of alumina, (c) at least one source of silica, and (d) a structure directing agent (SDA) comprising trimethyl (cyclohexylmethyl) ammonium cation: and 
 b. forming molecular sieve crystals having a CHA framework and the structure directing agent, and 
 
       recovering at least a portion of the molecular sieve crystals from the mother liquor. 
     
     
       29. A method for treating an exhaust gas comprising contacting a combustion exhaust gas containing NO x  and/or NH 3  with a catalyst according to  claim 12  to selectively reduce at least a portion of the NO x  into N 2  and H 2 O and/or oxidize at least a portion of the NH 3 . 
     
     
       30. A method of converting methanol to an olefin (MTO), the method comprising contacting methanol with a catalyst according to  claim 12 . 
     
     
       31. The molecular sieve of  claim 3  wherein the molecular sieve contains a structure directing agent (SDA) which comprises trimethyl (cyclohexylmethyl) ammonium cation.